Fluoride ion electrochemical cell

ABSTRACT

Electrochemical cells of the present invention are versatile and include primary and secondary cells useful for a range of important applications including use in portable electronic devices. Electrochemical cells of the present invention also exhibit enhanced safety and stability relative to conventional state of the art primary lithium batteries and lithium ion secondary batteries. For example, electrochemical cells of the present invention include secondary electrochemical cells using anion charge carriers capable of accommodation by positive and negative electrodes comprising anion host materials, which entirely eliminate the need for metallic lithium or dissolved lithium ion in these systems.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.11/681,493, filed on Mar. 2, 2007 which claims priority under 35 U.S.C.119(e) to U.S. provisional Patent Application 60/779,054 filed Mar. 3,2006, U.S. provisional Patent Application No. 60/897,310, filed Jan. 25,2007, and U.S. Provisional Application No. 60/900,409, filed Feb. 9,2007. Each of these applications is incorporated by reference in itsentirety to the extent not inconsistent with the disclosure herein.

U.S. application Ser. No. 11/681,493 is also a continuation-in-part ofU.S. application Ser. No. 11/677,541, filed Feb. 21, 2007, which is acontinuation in part of U.S. application Ser. No. 11/422,564, filed Jun.6, 2006, which claims the benefit of U.S. Provisional Application60/724,084, filed Oct. 5, 2005 and is a continuation in part of U.S.application Ser. No. 11/253,360 filed Oct. 18, 2005, which also claimsthe benefit of U.S. Provisional Application 60/724,084, filed Oct. 5,2005. Ser. No. 11/677,541 is also a continuation in part of U.S.application Ser. No. 11/675,308 and International ApplicationPCT/US2007/62243, both filed Feb. 15, 2007, both of which claim thebenefit of U.S. Provisional Applications 60/774,262, filed Feb. 16,2006, 60/784,957, filed Mar. 21, 2006 and 60/784,960, filed Mar. 20,2006. Ser. No. 11/677,541 also claims the benefit of U.S. ProvisionalApplications No. 60/775,110, filed Feb. 21, 2006, 60/775,559, filed Feb.22, 2006, and U.S. Provisional Application No. 60/900,409 filed Feb. 9,2007. Each of these applications is incorporated by reference in itsentirety to the extent not inconsistent with the disclosure herein.

U.S. application Ser. No. 11/681,493 is also a continuation-in-part ofU.S. application Ser. No. 11/560,570, filed Nov. 16, 2006, which claimspriority from U.S. Provisional Application Nos. 60/737,186, 60/775,110,60/775,559 filed Nov. 16, 2005, Feb. 21, 2006 and Feb. 22, 2006,respectively. Each of these applications is incorporated by reference inits entirety to the extent not inconsistent with the disclosure herein.

U.S. application Ser. No. 11/681,493 is also a continuation-in-part ofPCT International Application No. PCT/US2007/063094, filed on Mar. 1,2007.

BACKGROUND OF INVENTION

Over the last few decades revolutionary advances have been made inelectrochemical storage and conversion devices expanding thecapabilities of these systems in a variety of fields including portableelectronic devices, air and space craft technologies, and biomedicalinstrumentation. Current state of the art electrochemical storage andconversion devices have designs and performance attributes that arespecifically engineered to provide compatibility with a diverse range ofapplication requirements and operating environments. For example,advanced electrochemical storage systems have been developed spanningthe range from high energy density batteries exhibiting very low selfdischarge rates and high discharge reliability for implanted medicaldevices to inexpensive, light weight rechargeable batteries providinglong runtimes for a wide range of portable electronic devices to highcapacity batteries for military and aerospace applications capable ofproviding extremely high discharge rates over short time periods.

Despite the development and widespread adoption of this diverse suite ofadvanced electrochemical storage and conversion systems, significantpressure continues to stimulate research to expand the functionality ofthese systems, thereby enabling an even wider range of deviceapplications. Large growth in the demand for high power portableelectronic products, for example, has created enormous interest indeveloping safe, light weight primary and secondary batteries providinghigher energy densities. In addition, the demand for miniaturization inthe field of consumer electronics and instrumentation continues tostimulate research into novel design and material strategies forreducing the sizes, masses and form factors of high performancebatteries. Further, continued development in the fields of electricvehicles and aerospace engineering has also created a need formechanically robust, high reliability, high energy density and highpower density batteries capable of good device performance in a usefulrange of operating environments.

Many recent advances in electrochemical storage and conversiontechnology are directly attributable to discovery and integration of newmaterials for battery components. Lithium battery technology, forexample, continues to rapidly develop, at least in part, due to thediscovery of novel electrode and electrolyte materials for thesesystems. From the pioneering discovery and optimization of intercalationhost materials for positive electrodes, such as fluorinated carbonmaterials and nanostructured transition metal oxides, to the developmentof high performance non-aqueous electrolytes, the implementation ofnovel materials strategies for lithium battery systems haverevolutionized their design and performance capabilities. Furthermore,development of intercalation host materials for negative electrodes hasled to the discovery and commercial implementation of lithium ion basedsecondary batteries exhibiting high capacity, good stability and usefulcycle life. As a result of these advances, lithium based batterytechnology is currently widely adopted for use in a range of importantapplications including primary and secondary electrochemical cells forportable electronic systems.

Commercial primary lithium battery systems typically utilize a lithiummetal negative electrode for generating lithium ions which duringdischarge are transported through a liquid phase or solid phaseelectrolyte and undergo intercalation reaction at a positive electrodecomprising an intercalation host material. Dual intercalation lithiumion secondary batteries have also been developed, wherein lithium metalis replaced with a lithium ion intercalation host material for thenegative electrode, such as carbons (e.g., graphite, cokes etc.), metaloxides, metal nitrides and metal phosphides. Simultaneous lithium ioninsertion and de-insertion reactions allow lithium ions to migratebetween the positive and negative intercalation electrodes duringdischarge and charging. Incorporation of a lithium ion intercalationhost material for the negative electrode has the significant advantageof avoiding the use of metallic lithium which is susceptible to safetyproblems upon recharging attributable to the highly reactive nature andnon-epitaxial deposition properties of lithium.

The element lithium has a unique combination of properties that make itattractive for use in an electrochemical cell. First, it is the lightestmetal in the periodic table having an atomic mass of 6.94 AMU. Second,lithium has a very low electrochemical oxidation/reduction potential(i.e., −3.045 V vs. NHE (normal hydrogen reference electrode). Thisunique combination of properties enables lithium based electrochemicalcells to have very high specific capacities. Advances in materialsstrategies and electrochemical cell designs for lithium batterytechnology have realized electrochemical cells capable of providinguseful device performance including: (i) high cell voltages (e.g. up toabout 3.8 V), (ii) substantially constant (e.g., flat) dischargeprofiles, (iii) long shelf-life (e.g., up to 10 years), and (iv)compatibility with a range of operating temperatures (e.g., −20 to 60degrees Celsius). As a result of these beneficial characteristics,primary lithium-batteries are widely used as power sources in a range ofportable electronic devices and in other important device applicationsincluding, electronics, information technology, communication,biomedical engineering, sensing, military, and lighting.

State of the art lithium ion secondary batteries provide excellentcharge-discharge characteristics, and thus, have also been widelyadopted as power sources in portable electronic devices, such ascellular telephones and portable computers. U.S. Pat. Nos. 6,852,446,6,306,540, 6,489,055, and “Lithium Batteries Science and Technology”edited by Gholam-Abbas Nazri and Gianfranceo Pistoia, Kluer AcademicPublishers, 2004, are directed to lithium and lithium ion batterysystems which are hereby incorporated by reference in their entireties.

As noted above, lithium metal is extremely reactive, particularly withwater and many organic solvents, and this attribute necessitates use ofan intercalation host material for the negative electrode in secondarylithium based electrochemical cells. Substantial research in this fieldhas resulted in a range of useful intercalation host materials for thesesystems, such as LiC₆, Li_(x)Si, Li_(x)Sn and Li_(x)(CoSnTi). Use of anintercalation host material for the negative electrode, however,inevitably results in a cell voltage that is lower by an amountcorresponding to the free energy of insertion/dissolution of lithium inthe intercalation electrode. As a result, conventional state of the artdual intercalation lithium ion electrochemical cells are currentlylimited to providing average operating voltages less than or equal toabout 4 Volts. This requirement on the composition of the negativeelectrode also results in substantial loss in the specific energiesachievable in these systems. Further, incorporation of an intercalationhost material for the negative electrode does not entirely eliminatesafety risks. Charging these lithium ion battery systems, for example,must be carried out under very controlled conditions to avoidovercharging or heating that can result in decomposition of the positiveelectrode. Further, unwanted side reactions involving lithium ion canoccur in these systems resulting in the formation of reactive metalliclithium that implicate significant safety concerns. During charging athigh rates or at low temperatures, lithium deposition results indendrides formation that may grow across the separator and cause aninternal short-circuit within the cell, generating heat, pressure andpossible fire from combustion of the organic electrolyte and reaction ofmetallic lithium with air oxygen and moisture.

Dual-carbon cells have also been developed that utilize lithiuminsertion reactions for electrochemical storage, wherein anions andcations generated by dissolution of an appropriate electrolyte saltprovide the source of charge stored in the electrodes. During chargingof these systems, cations of the electrolyte, such as lithium ion (Li⁺),undergo insertion reaction at a negative electrode comprising acarbonaceous cation host material, and anions of the electrolyte, suchas PF₆ ⁻, undergo insertion reaction at a positive electrodecarbonaceous anion host material. During discharge, the insertionreactions are reversed resulting in release of cations and anions frompositive and negative electrodes, respectively. State of the artdual-carbon cells are unable to provide energy densities as large asthose provided by lithium ion cells, however, due to practicallimitations on the salt concentrations obtainable in these systems. Inaddition, some dual-carbon cells are susceptible to significant lossesin capacity after cycling due to stresses imparted by insertion andde-insertion of polyatomic anion charge carriers such as PF₆ ⁻. Further,dual-carbon cells are limited with respect to the discharge and chargingrates attainable, and many of these system utilize electrolytescomprises lithium salts, which can raise safety issues under someoperating conditions. Dual carbon cells are described in U.S. Pat. Nos.4,830,938; 4,865,931; 5,518,836; and 5,532,083, and in “Energy andCapacity Projections for Practical Dual-Graphite Cells”, J. R. Dahn andJ. A. Seel, Journal of the Electrochemical Society, 147 (3) 899-901(2000), which are hereby incorporated by reference to the extent notinconsistent with the present disclosure.

A battery consists of a positive electrode (cathode during discharge), anegative electrode (anode during discharge) and an electrolyte. Theelectrolyte contains ionic species that are the charge carriers.Electrolytes in batteries can be of several different types: (1) purecation conductors (e.g., beta Alumina conducts with Na⁺ only); (2) pureanion conductors (e.g., high temperature ceramics conduct with O⁻ or O²⁻anions only); and (3) mixed ionic conductors: (e.g., some Alkalinebatteries use a KOH aqueous solution that conducts with both OH⁻ and K⁺,whereas some lithium ion batteries use an organic solution of LiPF₆ thatconducts with both Li⁺ and PF₆ ⁻). During charge and dischargeelectrodes exchange ions with electrolyte and electrons with an externalcircuit (a load or a charger).

There are two types of electrode reactions.

1. Cation Based Electrode Reactions:

In these reactions, the electrode captures or releases a cation Y⁺ fromelectrolyte and an electron from the external circuit:

Electrode+Y⁺ +e ⁻→Electrode(Y).

Examples of cation based electrode reactions include: (i) carbon anodein a lithium ion battery: 6C+Li⁺+e⁻→LiC₆ (charge); (ii) lithium cobaltoxide cathode in a lithium ion battery: 2Li_(0.5)CoO₂+Li⁺+e⁻→2LiCoO₂(discharge); (iii) Ni(OH)₂ cathode in rechargeable alkaline batteries:Ni(OH)₂→NiOOH+H⁺+e⁻ (charge); (iv) MnO₂ in saline Zn/MnO₂ primarybatteries: MnO₂+H⁺+e⁻→HMnO₂ (discharge).

2. Anion Based Electrode Reactions:

In these reactions, the electrode captures or releases an anion X⁻ fromelectrolyte and an electron from the external circuit:

Electrode+X⁼→Electrode(X)+e ⁻

Examples of anion based electrode reactions include: (i) Cadmium anodein the Nickel-Cadmium alkaline battery: Cd(OH)₂+2e⁻→Cd+2OH⁻ (charge);and (ii) Magnesium alloy anode in the magnesium primary batteries:Mg+2OH⁻→Mg(OH)₂+2e⁻ (discharge).

Existing batteries are either of pure cation-type or mixed ion-typechemistries. To Applicants knowledge there are currently no knownbatteries having pure anion-type chemistry. Example of pure cation-typeand mixed ion-type batteries are provided below:

1. Pure Cation-Type of Battery:

Lithium ion batteries are an example of pure cation-type chemistry. Theelectrode half reactions and cell reactions for lithium ion batteriesare:

-   -   Carbon anode:

6C+Li⁺ +e ⁻→LiC₆ (charge)

-   -   lithium cobalt oxide cathode:

2Li_(0.5)CoO₂+Li⁺ +e ⁻→2LiCoO₂ (discharge)

-   -   cell reaction:

2LiCoO₂+6C→2Li_(0.5)CoO₂+LiC₆ (charge)

2Li_(0.5)CoO₂+LiC₆→2LiCoO₂+6C (discharge)

2. Mixed Ion-Type of Battery:

A Nickel/cadmium alkaline battery is an example of a mixed ion-type ofbattery. The electrode half reactions and cell reactions for aNickel/cadmium alkaline battery are provided below:

-   -   Ni(OH)₂ cathode (cation-type):

Ni(OH)₂→NiOOH+H⁺ +e ⁻ (charge)

-   -   Cadmium anode (anion-type):

Cd(OH)₂+2e ⁻→Cd+2OH⁻ (charge)

-   -   Cell reaction:

Cd(OH)₂+2Ni(OH)₂→Cd+2NiOOH+2H₂O (charge)

Cd+2NiOOH+2H₂O→Cd(OH)₂+2Ni(OH)₂ (discharge)

A Zn/MnO₂ battery is an example of a mixed ion-type of battery. Theelectrode half reactions and cell reactions for a Zn/MnO₂ battery areprovided below:

-   -   Zn anode (anion-type):

Zn+2OH⁻→ZnO+H₂O+2e ⁻ (discharge)

-   -   MnO₂ cathode (cation-type)

MnO₂+H⁺ +e ⁻→HMnO₂ (discharge)

-   -   Cell reaction:

Zn+2MnO₂+H₂O→ZnO+2HMnO₂ (discharge)

As will be clear from the foregoing, there exists a need in the art forsecondary electrochemical cells for a range of important deviceapplication including the rapidly increasing demand for high performanceportable electronics. Specifically, secondary electrochemical cells areneeded that are capable of providing useful cell voltages, specificcapacities and cycle life, while at the same time exhibiting goodstability and safety. A need exists for alternativeinsertion/intercalation based electrochemical cells that eliminate orreduce safety issues inherent to the use of lithium in primary andsecondary battery systems.

SUMMARY OF THE INVENTION

The present invention provides electrochemical cells capable of goodelectrical power source performance, particularly high specificenergies, useful discharge rate capabilities and good cycle life.Electrochemical cells of the present invention are versatile and includeprimary and secondary cells useful for a range of important applicationsincluding use in portable electronic devices. Electrochemical cells ofthe present invention also exhibit enhanced safety and stabilityrelative to conventional state of the art primary lithium batteries andlithium ion secondary batteries. For example, electrochemical cells ofthe present invention include secondary anionic electrochemical cellsusing anion charge carriers capable of accommodation by positive andnegative electrodes comprising anion host materials, which entirelyeliminate the need for metallic lithium or dissolved lithium ion inthese systems.

The present invention provides novel active electrode materialsstrategies, electrolyte compositions and electrochemical cell designsenabling a fundamentally new class of primary and secondaryelectrochemical cells. Anion charge carrier host materials for positiveand negative electrodes and high performance electrolytes are providedthat enable a new electrochemical cell platform capable of achievinguseful performance attributes, such as specific energies higher thanthat in conventional state of the art lithium ion batteries. In anembodiment, for example, the present invention provides combinations ofdifferent anion charge carrier host materials for positive and negativeelectrodes that enable secondary electrochemical cells capable ofexhibiting cell voltages greater than or equal to about 3.5 V. Inaddition, positive and negative electrode materials combinations of thepresent invention enable secondary electrochemical cells having a largecycle life and exhibiting good discharge stability upon cycling.Further, aqueous and nonaqueous electrolyte compositions are providedthat provide synergistic performance enhancements important forimproving device performance, stability and safety at high cellvoltages. For example, the present invention provides high performanceelectrolytes having anion receptors and/or cation receptors compatiblewith anion charge carrier active electrode host materials that providesecondary cells capable of stable discharge rates at high cell voltages.

In an aspect, the present invention provides an anionic electrochemicalcell utilizing an anion charge carrier capable of accommodation bypositive and negative electrodes comprising anion host materials. Thisaspect of the present invention includes both primary and secondaryelectrochemical cells. In an embodiment, an electrochemical cell of thisaspect of the present invention comprises a positive electrode; anegative electrode; and an electrolyte provided between the positiveelectrode and the negative electrode, wherein the electrolyte is capableof conducting anion charge carriers. The positive electrode and negativeelectrode of this embodiment comprise different anion host materialsthat reversibly exchange anion charge carriers with the electrolyteduring charging or discharging of the electrochemical cell. In thecontext of this description, the term “exchange” refers to release oraccommodation of anion charge carriers at the electrodes via oxidationand reduction reactions during discharge or charging of theelectrochemical cell. In this context, “accommodation” of anion chargecarriers includes capture of anion charge carriers by the host material,insertion of anion charge carriers into the host material, intercalationof anion charge carriers into the host material and/or chemical reactionof anion charge carriers with the host material. Accommodation includesalloy formation chemical reactions, surface chemical reactions with thehost material and/or bulk chemical reactions with the host material.

During discharge, reduction half reactions occurring at the positiveelectrode result in release of anion charge carriers from the positiveelectrode to the electrolyte, and oxidation half reactions occurring atthe negative electrode result in accommodation of anion charge carriersby the negative electrode. In these embodiments, therefore, anion chargecarriers are released from the positive electrode, migrate through theelectrolyte and are accommodated by the negative electrode duringdischarge of the electrochemical cell. This kinetic process is reversedduring charging in secondary electrochemical cells of the presentinvention. During charging in these embodiments, therefore, reductionhalf reactions occurring at the negative electrode result in release ofanion charge carriers to the electrolyte, and oxidation half reactionsoccurring at the positive electrode result in accommodation of anioncharge carriers from the electrolyte to the positive electrode.Accordingly, simultaneous release and accommodation of anion chargecarriers during discharge and charging of the electrochemical celloccurs as anion charge carriers are transported through the electrolyteand electrons are transported through an external circuit connectingpositive and negative electrodes.

Choice of the composition and phase of electrode host materials,electrolyte and anion charge carriers in this aspect of the invention isimportant in the present invention for accessing useful electrochemicalcell configurations. First, selection of the compositions of the anionhost materials for positive and negative electrodes and the anion chargecarrier determines, at least in part, the cell voltage of theelectrochemical cell. It is beneficial in some embodiments, therefore,to select an anion host material providing a sufficiently low standardelectrode potential at the negative electrode and to select an anionhost material providing a sufficiently high standard electrode potentialat the positive electrode so as to result in a cell voltage useful for agiven application. Second, selection of the compositions of the anionhost materials for positive and negative electrodes, electrolyte and theanion charge carrier establishes the kinetics at the electrode, and thusdetermines the discharge rate capabilities of the electrochemical cell.Third, use of electrode host materials, electrolyte and anion chargecarriers that do not result in fundamental structural changes ordegradation at the positive and negative electrodes during charging anddischarge is beneficial for secondary electrochemical cells exhibitinggood cycling performance.

In an embodiment of this aspect, the present invention provides fluorideion primary and secondary electrochemical cells having fluoride ions(F⁻¹) as the anion charge carriers. Electrochemical cell utilizingfluoride ion charge carriers of the present invention are referred to asfluoride ion electrochemical cells. Use of fluoride ion charge carriersin electrochemical cells of the present invention provides a number ofbenefits. First, the low atomic mass (18.998 AMU), high electronaffinity (−328 kJ mol⁻¹) of fluorine and about 6V redox voltagestability window (from −3.03V vs. NHE to +2.87V vs. NHE) of the fluorideion (F⁻) results in electrochemical cells having high voltage, highenergy densities and high specific capacities. Second, fluoride ion hasa small atomic radius and, thus, can participate in reversible insertionand/or intercalation reactions in many electrode host materials that donot result in significant degradation or significant structuraldeformation of the electrode host material upon cycling in secondaryelectrochemical cells. This property results in secondary fluoride ionelectrochemical cells having a large cycle life (e.g., greater than orequal to about 500 cycles). Third, fluoride ion is stable with respectto decomposition at electrode surfaces for a useful range of voltages(−3.03V vs. NHE to +2.87V vs. NHE), thereby providing enhancedperformance stability and safety of electrochemical cells. Fourth, asignificant number of fluoride ion host materials are available forpositive electrodes and negative electrodes that provide electrochemicalcells having large specific capacities and cell voltages.

As will be evident to one of skill in the art, the present inventionincludes, however, a wide range of anionic electrochemical cellconfigurations having anion charge carriers other than fluoride ions,including but not limited to:

BF₄ ⁻, PF₆ ⁻, AsF₆ ⁻, SbF₆ ⁻, BiF₆ ⁻, AlF₄ ⁻, GaF₄ ⁻, InF₄ ⁻, TlF₄ ⁻,SiF₅ ⁻, GeF₅ ⁻, SnF₅ ⁻, PbF₅ ⁻, SF₇ ⁻, IF₆ ⁻, ClO₄ ⁻, CF₃SO₃ ⁻,(CF₃SO₂)₂N⁻ and C₄F₉SO₃ ⁻Other anion charge carriers useful in electrochemical cells of thepresent invention include those having the formula: C_(n)F_(2n+1)BF₃ ⁻¹;wherein n is an integer greater than 1. Use of anion charge carriersother than fluoride ion requires incorporation of suitable hostmaterials for positive and negative electrodes capable of accommodationof the anion charge carrier during discharge and charging, and providinga desired cell voltage and specific capacity. In an embodiment, theanion charge carrier is an anion other than OH⁻ and HSO₄ ⁻, or SO₄ ²⁻.

In an embodiment, an electrolyte of a fluoride ion electrochemical cellof the present invention comprises a solvent and a fluoride salt,wherein the fluoride salt is at least partially present in a dissolvedstate in the electrolyte so as to generate fluoride ions in theelectrolyte. Electrolytes in electrochemical cells of the presentinvention include fluoride salts having the formula: MF_(n), wherein Mis a metal, and n is an integer greater than 0. In some embodiments, forexample, M is an alkali metal, such as Na, K or Rb, or M is an alkalineearth metal, such as Mg, Ca or Sr. In embodiments, M is a metal otherthan lithium so as to provide enhanced safety and stability relative toconventional state of the art lithium batteries and lithium ionbatteries. In some embodiments, the concentration of the fluoride saltin the electrolyte is selected from the range of about 0.1M to about2.0M.

Electrolytes for anionic electrochemical cells of the present invention,including fluoride ion electrochemical cells, include aqueouselectrolytes and nonaqueous electrolytes. Useful electrolytecompositions for anionic electrochemical cells preferably have one ormore of the following properties. First, electrolytes for someapplications preferably have a high ionic conductivity with respect tothe anion charge carrier, for example for fluoride ions. For example,some electrolytes useful in the present invention comprise solvents,solvent mixtures and/or additives providing conductivity for an anioncharge carrier, such as a fluoride ion anion charge carrier, greaterthan or equal to 0.0001 S cm⁻¹, greater than or equal to 0.001 S cm⁻¹,or greater than or equal to 0.005 S cm⁻¹. Second, electrolytes for someembodiments are capable of dissolving an electrolyte salt, such as afluoride salt, so as to provide a source of anion charge carriers at auseful concentration in the electrolyte. Third, electrolytes of thepresent invention are preferably stable with respect to decomposition atthe electrodes. For example, electrolytes of an embodiment of thepresent invention comprises solvents, electrolyte salts, additives andanion charge carriers that are stable at high electrode voltages, suchas a difference between positive and negative electrode voltages equalto or greater than about 4.5V. Fourth, electrolytes of the presentinvention preferable for some applications exhibit good safetycharacteristics, such as flame retardance.

Optionally, electrolytes of the present electrochemical cells includeone or more additives. In an embodiment, the electrolyte comprises ananion receptor, such as fluoride ion anion receptors capable ofcoordinating fluoride ions of a fluoride salt, and/or a cation receptor,for example a cation receptor capable of coordinating metal ions of afluoride salt. Useful anion receptors in the present invention include,but are not limited to, fluorinated boron-based anion receptors havingelectron withdrawing ligands, such as fluorinated boranes, fluorinatedboronates, fluorinated borates, phenyl boron-based compounds andaza-ether boron-based compounds. Useful cation receptors forelectrolytes of electrochemical cells of the present invention include,but are not limited to, crown ethers, lariat ethers, metallacrownethers, calixcrowns (e.g., calyx(aza)crowns), tetrathiafulvalene crowns,calixarenes, calix[4]arenediquinoes, tetrathiafulvalenes,bis(calixcrown)tetrathiafulvalenes, and derivatives thereof. In someembodiments, electrolytes of the present invention comprise otherinorganic, organic or gaseous additives. Additives in electrolytes ofthe present invention are useful for: (i) enhancing conductivity of theanion charge carrier, (ii) decreasing flammability, (iii) enhancingelectrode wetting, (iv) decreasing electronic conductivity, and (v)enhancing the kinetics of anion charge carriers at the electrodes, forexample by enhancing formation of a solid electrolyte interface (SEI) orby reducing the buildup of discharge products. In an embodiment, theelectrolyte comprises a Lewis acid or a Lewis base such as, but notlimited to:

BF₄ ⁻, PF₆ ⁻, AsF₆ ⁻, SbF₆ ⁻, BiF₆ ⁻, AlF₄ ⁻, GaF₄ ⁻, InF₄ ⁻, TlF₄ ⁻,SiF₅ ⁻, GeF₅ ⁻, SnF₅ ⁻, PbF₅ ⁻, SF₇ ⁻, IF₆ ⁻, ClO₄ ⁻, CF₃SO₃ ⁻,(CF₃SO₂)₂N⁻, C₄F₉SO₃ ⁻ and NR₄ ⁺ (R=H or an alkyl group C_(n)H_(2n+1)n=integer).

Active materials for positive and negative electrodes of fluoride ionelectrochemical cells of the present invention include fluoride ion hostmaterials capable of accommodating fluoride ions from the electrolyteduring discharge and charging of the electrochemical cell. In thiscontext, accommodation of fluoride ions includes insertion of fluorideions into the host material, intercalation of fluoride ions into thehost material and/or reaction of fluoride ions with the host material.Accommodation includes alloy formation reactions, surface reactionand/or bulk reactions with the host material. Use of fluoride ion hostmaterials that are capable of reversibly exchanging fluoride ions withthe electrolyte without significant degradation of the fluoride ion hostmaterial upon cycling is preferred for secondary fluoride ion batteriesof the present invention.

In an embodiment, a negative electrode of a fluoride ion electrochemicalcell of the present invention comprises a fluoride ion host material,such as a fluoride compound, having a low standard reduction potential,preferably less than or equal to about −1V for some applications, andmore preferably less than or equal to about −2 V for some applications.Useful fluoride ion host materials for negative electrodes ofelectrochemical cells of the present invention include, but are notlimited to: LaF_(x), CaF_(x), AlF_(x), EuF_(x), LiC₆, Li_(x)Si,Li_(x)Ge, Li_(x)(CoTiSn), SnF_(x), InF_(x), VF_(x), CdF_(x), CrF_(x),FeF_(x), ZnF_(x), GaF_(x), TiF_(x), NbF_(x), MnF_(x), YbF_(x), ZrF_(x),SmF_(x), LaF_(x) and CeF_(x). Preferred fluoride host materials fornegative electrodes of electrochemical cell are element fluoridesMF_(x), where M is an alkali-earth metal (Mg, Ca, Ba), M is a transitionmetal, M belongs to column 13 group (B, Al, Ga, In, Tl), or M is arare-earth element (atomic number Z between 57 and 71). The presentinvention also includes negative electrode fluoride ion host materialscomprising a polymer(s) capable of reversibly exchanging fluoride ionscomprising the anion ion charge carriers. Examples of such a conjugatedpolymers are, but not limited to: polyacetylene, polyaniline,polypyrrol, polythiophene and polyparaphenylene. Polymer materialsuseful for negative electrodes in the present invention are further setforth and described in Manecke, G. and Strock, W., in “Encyclopedia ofPolymer Science and Engineering, 2^(nd) Edition, Kroschwitz, J., I.,Editor. John Wiley, New York, 1986, vol. 5, pp. 725-755, which is herebyincorporated by reference to the extent not inconsistent with thedisclosure herein.

In an embodiment, a positive electrode of a fluoride ion electrochemicalcell of the present invention comprises a fluoride ion host material,such as a fluoride compound, having a high standard reduction potential,preferably for some applications greater than or equal to about 1V, andmore preferably for some applications greater than or equal to about 2V. In an embodiment, the fluoride ion host material of the positiveelectrode is an intercalation host material capable of accommodatingfluoride ions so as to generate a fluoride ion intercalation compound.“Intercalation” refers to refers to the process wherein an ion insertsinto a host material to generate an intercalation compound via ahost/guest solid state redox reaction involving electrochemical chargetransfer processes coupled with insertion of mobile guest ions, such asfluoride ions. Major structural features of the host material arepreserved after insertion of the guest ions via intercalation. In somehost materials, intercalation refers to a process wherein guest ions aretaken up with interlayer gaps (e.g., galleries) of a layered hostmaterial.

Useful fluoride ion host materials for positive electrodes ofelectrochemical cells of the present invention include, but are notlimited to, CFx, AgFx, CuFx, NiFx, CoFx, PbFx, CeFx, MnFx, AuFx, PtFx,RhFx, VFx, OsFx, RuFx and FeFx. In an embodiment, the fluoride ion hostmaterial of the positive electrode is a subfluorinated carbonaceousmaterial having a formula CFx, wherein x is the average atomic ratio offluorine atoms to carbon atoms and is selected from the range of about0.3 to about 1.0. Carbonaceous materials useful for positive electrodesof this embodiment are selected from the group consisting of graphite,coke, multiwalled carbon nanotubes, multi-layered carbon nanofibers,multi-layered carbon nanoparticles, carbon nanowhiskers and carbonnanorods. The present invention also includes positive electrodefluoride ion host materials comprising a polymer(s) capable ofreversibly exchanging fluoride ions comprising the anion ion chargecarriers. Examples of conjugated polymers for positive electrodesinclude, but not limited to: polyacetylene, polyaniline, polypyrrol,polythiophene and polyparaphenylene.

In an aspect, the present invention provides fluoride ionelectrochemical cells exhibiting enhanced device performance relative tostate of the art electrochemical cells such as lithium ion batteries.Certain fluoride ion host material-combinations for positive andnegative electrodes in fluoride ion electrochemical cells areparticularly beneficial for accessing useful device performance. Forexample, use of a subfluorinated CF_(x) positive electrode, wherein x isselected over the range of about 0.3 to 1, and a negative electrodecomprising LiC₆ or LaF_(x) is useful for accessing average operatingcell voltages greater than or equal to about 4 V, and in someembodiments greater than or equal to about 4.5 V. Other useful positiveelectrode host material/negative electrode host material combinations ofthe present invention providing good device performance includeCuFx/LaFx, AgFx/LaFx, CoFx/LaFx, NiFx/LaFx, MnFx/LaFx, CuFx/AIFx,AgFx/AIFx, NiFx/AIFx, NiFx/ZnFx, AgFx/ZnFx and MnFx/ZnFx (wherein theconvention is used corresponding to: [positive electrode hostmaterial]/[negative electrode host material] to set for the electrodecombination).

In an embodiment, a fluoride ion electrochemical cell of the presentinvention has an average operating cell voltage equal to or greater thanabout 3.5 V, and preferably for some applications an average operatingcell voltage equal to or greater than about 4.5 V. In an embodiment, afluoride ion electrochemical cell of the present invention has aspecific energy greater than or equal to about 300 Wh kg⁻¹, preferablygreater than or equal to about 400 Wh kg⁻¹. In an embodiment, thepresent invention provides a fluoride ion secondary electrochemical cellhaving a cycle life greater than or equal to about 500 cycles.

Useful solvents for electrolytes of the present invention are capable ofat least partially dissolving electrolyte salts, such as fluoride salts,and include, but are not limited to one or more solvent selected fromthe group consisting of propylene carbonate, nitromethane, Toluene(tol); ethylmethyl carbonate (EMC); Propylmethyl carbonate (PMC);Diethyl carbonate (DEC); Dimethyl carbonate (DMC); Methyl butyrate (MB,20° C.); n-Propyl acetate (PA); Ethyl acetate (EA); Methyl propionate(MP); Methyl acetate (MA); 4-Methyl-1,3-dioxolane (4MeDOL)(C₄H₈O₂);2-Methyltetrahydrofuran (2MeTHF)(C₅H₁₀O); 1,2 Dimethoxyethane (DME);Methyl formate (MF)(C₂H₄O₂); Dichloromethane (DCM); γ-Butyrolactone(γ-BL)(C₄H₆O₂); Propylene carbonate (PC)(C₄H₆O₃); Ethylene carbonate(EC, 40° C.)(C₃H₄O₃). Electrolytes, and components thereof, comprisingfull or partially fluorinated analogs of solvents, electrolyte salts andanion charge carriers are beneficial for some applications becausefluorination of these materials imparts enhanced stability with respectto decomposition at high electrode voltages and provides beneficialsafety characteristics, such as flame retardance. In the context of thisdescription, fluorine analogs include: (i) fully fluorinated analogswherein each hydrogen atom of the solvent, salt or anion charge carriermolecule is replaced by a fluorine atom, and (ii) partially fluorinatedanalogs wherein at least one hydrogen atom of the solvent, salt or anioncharge carrier molecule is replaced by a fluorine atom. Preferred anioncharge carrier in the electrolyte include, but not limited to:

F⁻, BF₄ ⁻, PF₆ ⁻, AsF₆ ⁻, SbF₆ ⁻, BiF₆ ⁻, AlF₄ ⁻, GaF₄ ⁻, InF₄ ⁻, TlF₄⁻, SiF₅ ⁻, GeF₅ ⁻, SnF₅ ⁻, PbF₅ ⁻, SF₇ ⁻, IF₆ ⁻, ClO₄ ⁻, CF₃SO₃ ⁻,(CF₃SO₂)₂N⁻ and C₄F₉SO₃ ⁻.

The following references describe electrolyte compositions useful inembodiments of the present invention, including fully fluorinated andpartially fluorinated solvents, salts and anion charge carriers, and arehereby incorporated by reference in their entireties to the extent notinconsistent with the present disclosure: (1) Li[C₂F₅BF₃] as anElectrolyte Salt for 4 V Class Lithium-Ion Cells, Zhi-Bin Zhou, Masayukitakeda, Takashi Fujii, Makoto Ue, Journal of Electrochemical Society,152(2):A351-A356, 2005; (2) Fluorinated Superacidic Systems, George A.Olah, Surya G. K. Prakash, Alain Goeppert, Actualite Chimique, 68-72Suppl. 301-302, October-November 2006; (3) Electrochemical properties ofLi[C_(n)F_(2n+1)BF₃] as Electrolyte Salts for Lithium-ion Cells, MakotoUe, Takashi Fujii, Zhi-Bin Zhou, Masayuki Takeda, Shinichi Kinoshita,Solid State Ionics, 177:323-331, 2006; (4) Anodic Stability of SeveralAnions Examined by AB Initio Molecular Orbital and Density FunctionalTheories, Makoto Ue, Akinori Murakami, Shinichiro Nakamura, Journal ofElectrochemical Society, 149(12):A1572-A1577, 2002; (5) Intrinsic AnionOxidation Potentials, Patrik Johansson, Journal of Physical Chemistry,110_(—)12077-12080, 2006; (6) Nonaqueous Liquid Electrolytes forLithium-based Rechargeable Batteries, Kang Xu, Chem. Rev.,104:4303-4417, 2004; (7) The Electrochemical Oxidation ofPolyfluorophenyltrifluoroborate Anions in Acetonitrile, Leonid A.Shundrin, Vadim V. Bardin, Hermann-Josef Frohn, Z. Anorg. Allg. Chem.630:1253-1257, 2004.

In another aspect, the present invention provides a method for making anelectrochemical cell comprising the steps of: (i) providing a positiveelectrode; (ii) providing a negative electrode; and (iii) providing anelectrolyte between the positive electrode and the negative electrode;the electrolyte capable of conducting anion charge carriers; wherein thepositive electrode and negative electrode are capable of reversiblyexchanging the anion charge carriers with the electrolyte duringcharging or discharging of the electrochemical cell.

In another aspect, the present invention provides a method forgenerating an electrical current, the method comprising the steps of:(i) providing an electrochemical cell; the electrochemical comprising: apositive electrode; a negative electrode; and an electrolyte providedbetween the positive electrode and the negative electrode; theelectrolyte capable of conducting anion charge carriers; wherein thepositive electrode and negative electrode are capable of reversiblyexchanging the anion charge carriers with the electrolyte duringcharging or discharging of the electrochemical cell; and (ii)discharging the electrochemical cell. The method of this aspect of thepresent invention may further comprise the step of charging theelectrochemical cell. In some embodiments of this aspect of the presentinvention the anion charge carrier is fluoride ion (F⁻).

In another aspect, the present invention provides a fluoride ionsecondary electrochemical cell comprising: (i) a positive electrodecomprising a first fluoride ion host material; said positive electrodehaving a first standard electrode potential; (ii) a negative electrodecomprising a second fluoride ion host material, said negative electrodehaving a second standard electrode potential, wherein the differencebetween said first standard electrode potential and said second standardelectrode potential is greater than or equal to about 3.5 V; and (iii)an electrolyte provided between said positive electrode and saidnegative electrode; said electrolyte capable of capable of conductingfluoride ion charge carriers, said electrolyte comprising a fluoridesalt and a solvent; wherein at least a portion of said fluoride salt ispresent in a dissolved state, thereby generating said fluoride ioncharge carriers in said electrolyte; wherein said positive electrode andnegative electrode are capable of reversibly exchanging said fluorideion charge carriers with said electrolyte during charging or dischargingof said electrochemical cell. In some embodiments of this aspect of thepresent invention the anion charge carrier is fluoride ion (F⁻).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1. FIG. 1A provides a schematic diagram illustrating a lithium ionbattery during charging and FIG. 1B provides a schematic diagramillustrating a lithium ion battery during discharge.

FIG. 2. A schematic diagram showing the average working potential ofdifferent negative electrode and positive electrode materials and cellvoltage for a conventional lithium ion battery.

FIG. 3. FIG. 3A provides a schematic diagram illustrating a fluoride ionbattery (FIB) of the present invention during discharge. FIG. 3Bprovides a schematic diagram showing the average working potential foran example embodiment corresponding to a LaF_(3-x) negative electrode, aCF_(x) positive electrode, and an electrolyte comprising MF provided inan organic electrolyte, wherein M is a metal such as K or Rb.

FIG. 4. FIG. 4 provides crystal structure of carbon fluoride.

FIG. 5. FIG. 5 provides -ray diffraction patterns (CuK_(α) □radiation)from various positive electrode materials evaluated. Diffractionpatterns for carbon nanofiber, KS15 and commercial CF₁ are shown in FIG.5.

FIG. 6. FIG. 6 provides discharge profiles for CF₁ positive electrodesat room temperature for a variety of discharge rates ranging from C/20to C.

FIG. 7. FIG. 7 provides discharge profiles for CF_(0.530), KS15 positiveelectrodes at room temperature for a variety of discharge rates rangingfrom C/20 to C.

FIG. 8. FIG. 8 provides discharge profiles for CF_(0.647), KS15 positiveelectrodes at room temperature for a variety of discharge rates rangingfrom C/20 to 6 C.

FIG. 9. FIG. 9 provides discharge profiles for CF_(0.21), carbonnanofiber positive electrodes at room temperature for a variety ofdischarge rates ranging from C/20 to 6 C.

FIG. 10. FIG. 10 provides discharge profiles for CF_(0.59), carbonnanofiber positive electrodes at room temperature for a variety ofdischarge rates ranging from C/20 to 6 C.

FIG. 11. FIG. 11 provides discharge profiles for CF_(0.76), carbonnanofiber positive electrodes at room temperature for a variety ofdischarge rates ranging from C/20 to 6 C.

FIG. 12. FIG. 12 provides discharge profiles for CF_(0.82), carbonnanofiber positive electrodes at room temperature for a variety ofdischarge rates ranging from C/20 to 4 C.

FIG. 13. FIG. 13 provides charge-discharge profiles for CF_(0.82),multiwalled nanotubes positive electrodes for a voltage range 1.5V to4.6V. Voltage is plotted on the Y axis (left side), Current is plottedon the Y axis (right side) and time is plotted on the X axis.

FIG. 14. FIG. 14 provides charge-discharge profiles for CF_(0.82),multiwalled nanotubes positive electrodes for a voltage range 1.5V to4.8V. Voltage is plotted on the Y axis (left side), Current is plottedon the Y axis (right side) and time is plotted on the X axis.

FIG. 15. FIG. 15 provides charge-discharge profiles for CF₁ positiveelectrodes for a voltage range 1.5V to 4.8V. Voltage is plotted on the Yaxis (left side), Current is plotted on the Y axis (right side) and timeis plotted on the X axis.

FIG. 16. FIG. 16 provides plots of voltage (V) vs. time (hours) for aLi/CF_(x) half cell configuration for 4.6V and 4.8V. An increase indischarge capacity of 0.25% is observed at 4.8V.

FIG. 17. FIG. 17 provides plots of voltage (V) vs relative capacity (%)for a Li/CF_(x) half cell configuration with a CF_(0.647) KS15 positiveelectrode for voltages ranging from 4.8V and 5.4V. As shown in FIG. 17,the CF_(0.647) KS15 positive electrode capacity increased with highercharge cutoff voltage over the range of 4.8V to 5.4V.

FIG. 18. FIG. 18 provides cycle capacity curves of discharge capacity(mAh/g-C) verse cycle number for various positive electrode materialsevaluated. This data demonstrates that 120 mAh/g-C rechargeable capacityhas been achieved in a Li/CF_(x) half cell configuration charged to 4.8V at a 2 C-rate.

FIG. 19. FIG. 19 provides plots of discharge cycle vs. cycle number forCF_(0.82), multiwalled nanotubes positive electrodes for voltages equalto 14.6V to 4.8V

FIG. 20. FIG. 20 provides a plot of the discharge rate capability for aLiMn₂O₄ positive electrode.

FIG. 21. FIG. 21A provides a plot of discharge voltage vs timeindicating two time points (1) and (2) for which x-ray diffractionpatterns were taken. Thin graphite electrodes were used (50 micronsthick 3-4 mg). FIG. 21B shows x-ray diffraction patterns acquired at twotime points (1) and (2) shown in FIG. 21A. FIG. 21C shows x-raydiffraction patterns acquired at two time points (1) and (2) shown inFIG. 21A on an enlarge scale. The diffraction patterns in FIGS. 21B and21C show stage formation of intercalated fluoride ions (a mixture ofstage 2 and stage 3). Also shown in The diffraction patterns in FIGS.21B and 21C is that the graphite phase completely disappeared at 5.2Vand reappeared at 3.2V.

FIG. 22. Provides Electron Energy Loss Spectrum (EELS) of the positiveelectrode material charged to 5.2V. Only pure fluorine was detected inthe sample, and no other species such as B or P are present indicatingother anions in the electrolyte were not intercalated.

DETAILED DESCRIPTION OF THE INVENTION

Referring to the drawings, like numerals indicate like elements and thesame number appearing in more than one drawing refers to the sameelement. In addition, hereinafter, the following definitions apply:

“Standard electrode potential” (E°) refers to the electrode potentialwhen concentrations of solutes are 1M, the gas pressures are 1 atm andthe temperature is 25 degrees Celsius. As used herein standard electrodepotentials are measured relative to a standard hydrogen electrode.

“Anion charge carrier” refers to a negatively charge ion provided in anelectrolyte of an electrochemical cell that migrates between positiveand negative electrodes during discharge and charging of theelectrochemical cell. Anion charge carriers useful in electrochemicalcells of the present invention include, but are not limited to, fluorideions (F), and the following other anions:

BF₄ ⁻, PF₆ ⁻, AsF₆ ⁻, SbF₆ ⁻, BiF₆ ⁻, AlF₄ ⁻, GaF₄ ⁻, InF₄ ⁻, TlF₄ ⁻,SiF₅ ⁻, GeF₅ ⁻, SnF₅ ⁻, PbF₅ ⁻, SF₇ ⁻, IF₆ ⁻, ClO₄ ⁻, CF₃SO₃ ⁻,(CF₃SO₂)₂N⁻ and C₄F₉SO₃ ⁻

“Fluoride ion host material” refers to a material capable ofaccommodating fluoride ions. In this context, accommodating includesinsertion of fluoride ions into the host material, intercalation offluoride ions into the host material and/or reaction of fluoride ionswith the host material. Fluoride ion host materials useful for positiveor negative electrodes in electrochemical cells of the present inventioninclude, but are not limited to, LaF_(x), CaF_(x), AlF_(x), EuF_(x),LiC₆, Li_(x)Si, Li_(x)Ge, Li_(x)(CoTiSn), SnF_(x), InF_(x), VF_(x),CdF_(x), CrF_(x), FeF_(x), ZnF_(x), GaF_(x), TiF_(x), NbF_(x), MnF_(x),YbF_(x), ZrF_(x), SmF_(x), LaF_(x) and CeF_(x), CFx, AgFx, CuFx, NiFx,CoFx, PbFx, CeFx, MnFx, AuFx, PtFx, RhFx, VFx, OsFx, RuFx and FeFx.Preferred fluoride host materials for negative electrodes ofelectrochemical cell are element fluorides MF_(x), where M is analkali-earth metal (Mg, Ca, Ba), M is a transition metal, M belongs tocolumn 13 group (B, Al, Ga, In, Tl) or M is a rare-earth element (atomicnumber Z between 57 and 71).

“Intercalation” refers to refers to the process wherein an ion insertsinto a host material to generate an intercalation compound via ahost/guest solid state redox reaction involving electrochemical chargetransfer processes coupled with insertion of mobile guest ions, such asfluoride ions. Major structural features of the host material arepreserved after insertion of the guest ions via intercalation. In somehost materials, intercalation refers to a process wherein guest ions aretaken up with interlayer gaps (e.g., galleries) of a layered hostmaterial. Examples of intercalation compounds include fluoride ionintercalation compounds wherein fluoride ions are inserted into a hostmaterial, such as a layered fluoride host material or carbon hostmaterial. Host materials useful for forming intercalation compounds forelectrodes of the present invention include, but are not limited to,CF_(x), FeFx, MnFx, NiFx, CoFx, LiC6, LixSi, and LixGe.

The term “electrochemical cell” refers to devices and/or devicecomponents that convert chemical energy into electrical energy orelectrical energy into chemical energy. Electrochemical cells have twoor more electrodes (e.g., positive and negative electrodes) and anelectrolyte, wherein electrode reactions occurring at the electrodesurfaces result in charge transfer processes. Electrochemical cellsinclude, but are not limited to, primary batteries, secondary batteriesand electrolysis systems. General cell and/or battery construction isknown in the art, see e.g., U.S. Pat. Nos. 6,489,055, 4,052,539,6,306,540, Seel and Dahn J. Electrochem. Soc. 147(3) 892-898 (2000).

The term “capacity” is a characteristic of an electrochemical cell thatrefers to the total amount of electrical charge an electrochemical cell,such as a battery, is able to hold. Capacity is typically expressed inunits of ampere-hours. The term “specific capacity” refers to thecapacity output of an electrochemical cell, such as a battery, per unitweight. Specific capacity is typically expressed in units ofampere-hours kg⁻¹.

The term “discharge rate” refers to the current at which anelectrochemical cell is discharged. Discharge current can be expressedin units of ampere-hours. Alternatively, discharge current can benormalized to the rated capacity of the electrochemical cell, andexpressed as C/(X t), wherein C is the capacity of the electrochemicalcell, X is a variable and t is a specified unit of time, as used herein,equal to 1 hour.

“Current density” refers to the current flowing per unit electrode area.In some embodiments, the positive electrode, negative electrode or bothare nanostructured materials. The term “nanostructured” refers materialsand/or structures have a plurality of discrete structural domains withat least one physical dimension (e.g., height, width, length, crosssectional dimension) that is less than about 1 micron. In this context,structural domains refer to features, components or portions of amaterial or structure having a characteristic composition, morphologyand/or phase. Nanostructured materials useful as positive electrodeactive materials include nanostructured composite particles having aplurality of fluorinated carbon domains and unfluorinated carbondomains. In some embodiments, nanostructured materials of the presentinvention comprise a plurality of structural domains having differentcompositions, morphologies and/or phase intermixed on a very fine scale(e.g., at least smaller than 10's of nanometers). Nanostructuredmaterials useful as negative electrode active materials includenanostructured composite particles having a plurality of fluorinatedmetal domains and unfluorinated metal domains. Preferred nanostrcturedfluorinated metal host materials for negative electrodes ofelectrochemical includes but not limited to alkali-earth metals (Mg, Ca,Ba), transition metals, column 13 group elements (B, Al, Ga, In, TI) andrare-earth metals (atomic number Z between 57 and 71). In someembodiments, nanostructured materials for negative electrodes of thepresent invention comprise a plurality of structural domains havingdifferent compositions, morphologies and/or phase intermixed on a veryfine scale (e.g., at least smaller than 10's of nanometers).

“Active material” refers to the material in an electrode that takes partin electrochemical reactions which store and/or delivery energy in anelectrochemical cell.

As used herein, the expression “subfluorinated carbonaceous material”refers to a multiphase carbonaceous material having an unfluorinatedcarbonaceous component. As used herein an “unfluorinated carbonaceouscomponent” includes unfluorinated carbon compositions and/or phases,such as graphite, coke, multiwalled carbon nanotubes, carbon nanofibers,carbon nanowhiskers, multi-layered carbon nanoparticles, carbonnanowhiskers, and carbon nanorods, and also includes slightlyfluorinated carbon compositions and/or phases. Slightly fluorinated, inthis context, refers to carbon that is weakly bound to fluorine, asopposed to compositions wherein carbon is covalently bonded to fluorine,as in CF₁ and C₂F phases. Multiphase subfluorinated carbonaceousmaterials may comprises a mixture of carbonaceous phases including, oneor more unfluorinated carbonaceous phases, and one or more fluorinatedphase (e.g., poly(carbon monofluoride (CF₁); poly(dicarbon monofluoride)etc.). Subfluorinated carbonaceous materials include nanostructuredmaterials having fluorinated and unfluorinated domains. Subfluorinatedcarbonaceous materials include carbonaceous materials exposed to afluorine source under conditions resulting in incomplete or partialfluorination of a carbonaceous starting material. Subfluorinatedcarbonaceous materials useful in the present invention and relatedmethods of making subfluorinated carbonaceous materials are described inU.S. patent application Ser. Nos. 11/253,360, 11/422,564 and 11/560,570filed Oct. 18, 2005, Jun. 6, 2006, and Nov. 16, 2006, respectively,which are hereby incorporated by reference in their entirety to theextent not inconsistent with the present description. A range ofcarbonaceous materials are useful for subfluorinated active materials inpositive electrodes of the present invention including graphite, coke,and carbonaceous nanomaterials, such as multiwalled carbon nanotubes,carbon nanofibers, multi-layered carbon nanoparticles, carbonnanowhiskers and carbon nanorods.

As used herein, a carbon nanomaterial has at least one dimension that isbetween one nanometer and one micron. In an embodiment, at least onedimension of the nanomaterial is between 2 nm and 1000 nm. For carbonnanotubes, nanofibers, nanowhiskers or nanorods the diameter of thetube, fiber, nanowhiskers or nanorod falls within this size range. Forcarbon nanoparticles, the diameter of the nanoparticle falls within thissize range. Carbon nanomaterials suitable for use with the inventioninclude materials which have total impurity levels less than 10% andcarbon materials doped with elements such as boron, nitrogen, silicon,tin and phosphorous.

As used herein, the term “nanotube” refers to a tube-shaped discretefibril typically characterized by a diameter of typically about 1 nm toabout 20 nm. In addition, the nanotube typically exhibits a lengthgreater than about 10 times the diameter, preferably greater than about100 times the diameter. The term “multi-wall” as used to describenanotubes refers to nanotubes having a layered structure, so that thenanotube comprises an outer region of multiple continuous layers ofordered atoms and a distinct inner core region or lumen. The layers aredisposed substantially concentrically about the longitudinal axis of thefibril. For carbon nanotubes, the layers are graphene layers. Carbonnanotubes have been synthesized in different forms as Single-, Double-and Multi-Walled Carbon Nanotubes noted SWCNT, DWCNT and MWCNTrespectively. The diameter size ranges between about 2 nm in SWCNTs andDWCNTs to about 20 nm in MWCNTs. In an embodiment, the MWNT used in theinvention have a diameter greater than 5 nm, greater than 10 nm, between10 and 20 nm, or about 20 nm.

Electrode refers to an electrical conductor where ions and electrons areexchanged with electrolyte and an outer circuit. “Positive electrode”and “cathode” are used synonymously in the present description and referto the electrode having the higher electrode potential in anelectrochemical cell (i.e. higher than the negative electrode).“Negative electrode” and “anode” are used synonymously in the presentdescription and refer to the electrode having the lower electrodepotential in an electrochemical cell (i.e. lower than the positiveelectrode). Cathodic reduction refers to a gain of electron(s) of achemical species, and anodic oxidation refers to the loss of electron(s)of a chemical species. Positive electrodes and negative electrodes ofthe present electrochemical cell may further comprises a conductivediluent, such as acetylene black, carbon black, powdered graphite, coke,Carbon fiber, and metallic powder, and/or may further comprises abinder, such polymer binder. Useful binders for positive electrodes insome embodiments comprise a fluoropolymer such as polyvinylidenefluoride (PVDF). Positive and negative electrodes of the presentinvention may be provided in a range of useful configurations and formfactors as known in the art of electrochemistry and battery science,including thin electrode designs, such as thin film electrodeconfigurations. Electrodes are manufactured as disclosed herein and asknown in the art, including as disclosed in, for example, U.S. Pat. Nos.4,052,539, 6,306,540, 6,852,446. For some embodiments, the electrode istypically fabricated by depositing a slurry of the electrode material,an electrically conductive inert material, the binder, and a liquidcarrier on the electrode current collector, and then evaporating thecarrier to leave a coherent mass in electrical contact with the currentcollector.

“Electrode potential” refers to a voltage, usually measured against areference electrode, due to the presence within or in contact with theelectrode of chemical species at different oxidation (valence) states.

“Electrolyte” refers to an ionic conductor which can be in the solidstate, the liquid state (most common) or more rarely a gas (e.g.,plasma).

“Cation” refers to a positively charged ion, and “anion” refers to anegatively charged ion.

The present invention provides primary and secondary anionicelectrochemical cells utilizing fluoride ion charge carriers and activeelectrode materials comprising fluoride ion host materials that providesan alternative to conventional state of the art lithium batteries andlithium ion batteries. Advantages of the present electrochemical cellsover lithium based systems include accessing higher specific capacities,larger average operating voltages and improving safety.

Anionic electrochemical cells of the present invention, includingfluoride ion electrochemical cells, operate on the principle ofsimultaneous oxidation and reduction reactions that involveaccommodation and release of anion charge carriers by positive andnegative electrodes comprising different anion charge carrier hostmaterials. In these systems, anion charge carriers shuttle back andforth between positive and negative electrodes during discharge andcharging of the anionic electrochemical cell.

The following electrode half reactions, cells reactions and electrolytereactions are provided to set forth and describe the fundamentalprinciples by which anionic electrochemical cells of the presentinvention operate.

1. Electrode Reactions

A⁻ is the anion charge carrier, PA_(n) is the positive electrode anionhost material and NA_(m) is the negative electrode anion host material.In a primary battery, only discharge reactions occur:

-   -   At the positive electrode, A⁻ is released:

-   -   At the negative electrode, A⁻ is occluded

Accordingly, the cell overall reaction is:

In a rechargeable battery, equations (1) and (2) are reversed duringcharge, therefore the overall cell reaction is:

2. Electrolyte Formation Reactions:

The present invention includes several sources of dissolved A⁻ anion inan electrolyte provide between positive and negative electrodes:

-   -   (i) A soluble compound such as a salt C_(q)A_(p): where C is a        monovalent, divalent, a trivalent, multivalent cation (C^(n+),        1≦n≦6). For example, if C is monovalent cation the salt        dissolution equilibrium is written as:

C_(q)A_(p)

qC⁺ +pA⁻ (here p=q)  (5)

-   -   -   Here the use of a cation receptor R and/or an anion receptor            R′ may enhance the solubility:

C_(q)A_(p) +zqR

qCR_(z) ⁺ +pA⁻  (6)

C_(q)A_(p) +z′pR′

qC⁺ +pAR′_(z′) ⁻  (7)

-   -   (ii) A soluble anion XA_(p) ⁻ that releases A⁻:

XA_(p) ⁻

XA_(p-1)+A⁻  (8)

Optionally a cation receptor R and/or an anion receptor R′ may beprovide in the electrolyte to enhance the solubility of A⁻.

As an example of these concepts, provided below are the half reactions,cell reaction and electrolyte reactions for discharge of a fluoride ionelectrochemical cell of the present invention comprising a LiC₆ negativeelectrode, a CFx positive electrode and a F⁻ conductive electrolyte.

Discharge Reactions:

negative electrode: LiC₆+F⁻→6C+LiF+e ⁻ (negative electrode accommodatesF during discharge)

positive electrode: CFx+xe ⁻→C+xF⁻ (positive electrode releases F duringdischarge)

cell reaction: xLiC₆+CFx→(1+6x)C+xLiF

-   -   (F⁻ is transferred between positive electrode and negative        electrode during discharge)        Electrolyte: Optionally, two types of reactions can enhance the        F⁻ dissolution:

LiF+yLA→Li⁺+(LA)_(y)F⁻, or

LiF+zLB→Li(LB)_(z) ⁺+F⁻

(LA=Lewis acid such as PF₅, BF₃ or an anion receptor, LB=Lewis base suchas PF₆ ⁻, BF₄ ⁻ or a cation receptor: i.e. crown ether).

To further describe and set forth the anionic electrochemical cells ofthe present invention, the discussion below draws a comparison of thepresent systems with conventional lithium ion battery technology. Atypical lithium ion battery (LIB) comprises three fundamental elements:(1) a carbon-based negative electrode (anode), (2) lithium cation (Li+)conducting electrolyte, and (3) a transition metal oxide positiveelectrode (cathode) (e.g., LiCoO₂). Lithium cation (Li+) is the chargecarrier in these systems, and these electrochemical cells function viasimultaneous insertion and de-insertion reactions occurring at positiveand negative electrodes in concert with electron transport betweenelectrodes. During charge and discharge of a lithium ion battery, Li+ions are shuttled between the negative and positive electrode. Thereversible dual intercalation mechanism of these batteries gives rise tothe term “rocking chair” or “shuttle-cock” batteries.

FIG. 1A provides a schematic diagram illustrating a lithium ion batteryduring charging. During charging lithium ions are released from thepositive electrode (i.e., designated as cathode in FIG. 1A), migratethrough the electrolyte and are accommodated by the negative electrode(i.e., designated as anode in FIG. 1A). As shown in FIG. 1A, thedirection of the flow of electrons during charging is from the positiveelectrode to the negative electrode. FIG. 1B provides a schematicdiagram illustrating a lithium ion battery during discharge. Duringdischarge, lithium ions are released from the negative electrode (i.e.,designated as anode in FIG. 1B), migrate through the electrolyte and areaccommodated by the positive electrode (i.e., designated as cathode inFIG. 1B). As shown in FIG. 1B, the direction of the flow of electronsduring charging is from the negative electrode to the positiveelectrode.

FIG. 2 provides schematic diagram showing the average working potentialof different negative electrode and positive electrode materials andcell voltage for a conventional lithium ion battery. The averageoperating voltage of the electrochemical cell arises, in part, from thedifference between the chemical potential of Li⁺ ion in the negative andpositive electrodes. In the example shown in FIG. 2, the difference inthe electrode potentials of Li_(x)C₆ and Li_(x)CoO₂ is approximately 4V.The LIB cell extended reaction for this example is:

2LiCoO₂+6C

2Li_(0.5)CoO₂+LiC₆

The theoretical energy density of this example LIB system can becalculated as follows:

${E\left( {L\; I\; B} \right)} = {\frac{F\left( {O\; C\; V} \right)}{3.6\left\lbrack \left( {{2{M\left( {LiCoO}_{2} \right)}} + {6{M(C)}}} \right\rbrack \right.} = {\frac{96500 \times 4.2}{3.6 \times \left( {196 + 72} \right)} = {420\mspace{14mu} {Wh}\text{/}{kg}}}}$

In electrochemical cells of the present invention the charge carrier isa negatively charged anion. In fluoride ion electrochemical cells, forexample, the anion charge carrier is fluoride ion (F⁻¹). Similar tolithium ion batteries, fluoride ion electrochemical cells of the presentinvention operate on the principle of simultaneous fluoride ioninsertion and de-insertion reactions occurring at positive and negativeelectrodes in concert with electron transport between electrodes. Duringcharge and discharge of a fluoride ion electrochemical cell, F ions areshuttled between the negative and positive electrodes.

FIG. 3A provides a schematic diagram illustrating a fluoride ionelectrochemical cell during discharge. During discharge fluoride anionsare released from the positive electrode (i.e., designated as cathode inFIG. 3A), migrate through the electrolyte and are accommodated by thenegative electrode (i.e., designated as anode in FIG. 3A). As shown inFIG. 3A, the direction of the flow of electrons during discharge is fromthe negative electrode to the positive electrode. During charging of afluoride ion electrochemical cell, fluoride anions are released from thenegative electrode migrate through the electrolyte and are accommodatedby the positive electrode. The direction of the flow of electrons duringcharging is from the positive electrode to the negative electrode.Release and accommodation of fluoride ions during discharge and chargingresults from oxidation and reduction reactions occurring at theelectrodes.

Similar to the description above relating to lithium ion batteries, theopen-circuit voltage in a fluoride ion electrochemical cell results, atleast in part, from differences in the chemical potential of thefluoride ions in the negative electrode and the positive electrode. Thepositive electrode and negative electrode are respectively a highvoltage and a low voltage fluorides, able to reversible exchange F⁻ withelectrolyte, for example:

-   -   Positive electrode: CF_(x), AgF_(2-x), CuF_(3-x), NiF_(3-x), . .        .    -   Negative electrode: LaF_(3-x), CaF_(2-x), AlF_(3-x), EuF_(3-x),        . . .

FIG. 3B provides a schematic diagram showing the average workingpotential for an example embodiment corresponding to a LaF_(3-x)negative electrode, a CF_(x) positive electrode, and an electrolytecomprising MF provided in an organic electrolyte, wherein M is a metalsuch as K or Rb. The relevant parameters, half reactions and cellreaction are summarized below for this example:

Negative electrode: LaF₃,

Positive electrode: CF_(y)

Electrolyte: MF in organic electrolyte (M=K, Rb, . . . )

Electrode Reactions:

Negative electrode: LaF₃+3xe ⁻

LaF_(3(1−x))+3xF⁻ (x≦1)  (9)

Positive electrode: 3CF_(y)+3xF⁻

3CF_(x+y)+3xe ⁻ (y≦1−x)  (10)

Cell Reaction:

LaF₃+3CF_(y)

LaF_(3(1−x))+3CF_(x+y)  (11)

As shown in FIG. 3B, the difference in the electrode potentials for thisexample is about 4.5 V. The theoretical cell voltage takes into accountthe La³⁺/La and the CF_(x)/F⁻ redox couples and the open circuit voltageOCV at the end of charge is expected to be approximately 4.5V, which islarger than that of a conventional lithium ion battery (see calculationabove). The theoretical energy density for this example fluoride ionbattery (FIB) system can be calculated as follows:

The FIB Energy Density:

With cell reaction (3) and x=1, y=0; (LaF₃+3CF_(y)

LaF_(3(1−x))+3CF_(x+y)),

The theoretical energy density is:

${E\left( {F\; I\; B} \right)} = {\frac{2{F\left( {O\; C\; V} \right)}}{3.6\left\lbrack {{M\left( {LaF}_{3} \right)} + {3{M(C)}}} \right\rbrack} = {\frac{3 \times 96500 \times 4.5}{3.6 \times \left( {196 + 36} \right)} = {1560\mspace{14mu} {Wh}\text{/}{kg}}}}$

This calculation give rise of a ratio of the theoretical energy densityfor the example fluoride ion electrochemical cell and the examplelithium ion battery described above equal to 3.7:

$\frac{E\left( {F\; I\; B} \right)}{E\left( {L\; I\; B} \right)} = {\frac{1560}{420} = {3.7x}}$

Table 1 provides a comparison of the performance attributes andcompositions of lithium ion batteries and the fluoride ionelectrochemical cells described above. Benefits of the present fluorideion batteries (FIBs) include: (i) enhanced safety of the fluoride ionelectrochemical cell, (ii) higher operating voltage of the fluoride ionelectrochemical cell; (iii) larger energy density in the fluoride ionelectrochemical cell; and (iv) lower costs of the fluoride ionelectrochemical cell.

TABLE 1 Comparison of the performance attributes and compositions oflithium ion batteries and the fluoride ion electrochemical cells LIB FIBComments Positive LiCoO2, CF_(x), AgF_(x), CuF_(x), Solid fluorides areelectrode Li(NiCoMn)O₂, NiF_(x) more stable than LiFePO₄ oxides NegativeLiC₆, LaF_(x), EuF_(x), LiC₆ High capacity electrode LixSi, LixSn,negative electrodes Lix(CoSnTi) in FIBs Electrolyte LiPF₆ in EC- MF inPC or Cheap and more DME-DMC nitromethane stable electrolyte (M = Li, K,Rb) in FIB Voltage 3-5 V 3.5-5.5 V Higher operating (V) voltage. Highstability at high voltages Energy 340 Wh/kh 1560 (Theor.) of the 3.7xenergy density (Theor.) LaF₃/CF_(x) couple in FIBs Safety Lithium isFluorides are very Increased safety due unstable stable. No soluble tomore robust metal used chemistry Cost High when Except for Ag, most FIBshould be 4-5x Co is used positive electrodes cheaper in $/Wh andnegative electrodes are cheap

Fluoride Ion batteries (FIBs) are pure anion-type batteries where theanode and the cathode reactions involve fluoride anion F⁻ accommodationand release. FIBs can be primary batteries and rechargeable batteriesdepending on the reversibility of the electrode reactions. However, bothprimary and rechargeable FIBs require a F⁻ anion conductive electrolyte.Fluoride ion batteries can be further categorized into two classes.

In the first class, both positive and negative electrodes containfluoride anions. A fluoride ion electrochemical cell having a LaF₃ anodeand a CF_(x) cathode is an example of this first class. The electrodehalf reactions and cell reactions for the (LaF₃/CF_(x)) system are:

LaF₃ Anode:

LaF₃+3ye ⁻→LaF_(3(1−y))+3yF⁻ (charge)

CF_(x) Cathode:

CF_(x) +xe ⁻→C+xF⁻ (discharge)

Cell Reaction:

xLaF₃+3yC→xLaF_(3(1−y))+3yCF_(x) (charge)

xLaF_(3(1−y))+3yCF_(x) →xLaF₃+3yC

Other examples of this first class of the fluoride ion electrochemicalcell include, but are not limited to, (anode/cathode) couples:(LaF₃/AgF_(x)), (LaF₃/NiF_(x)), (EuF₃/CF_(x)), (EuF₃/CuF_(x))

In the second class, only one electrode contains fluoride anions. Afluoride ion electrochemical cell having a LiC₆ anode and a CF_(x)cathode is an example of this second class. The electrode half reactionsand cell reactions for the (LiC₆/CF_(x)) system are:

LiC₆ Anode:

LiC₆+F⁻→6C+LiF+e ⁻ (discharge)

CF_(x) Cathode:

CF_(x) +xe ⁻→C+xF (discharge)

Cell Reaction:

xLiC₆+CF_(x)→(6x+1)C+xLiF (discharge)

(6x+1)C+xLiF→xLiC₆+CF_(x) (charge)

Other examples of this first class of the fluoride ion electrochemicalcell include, but are not limited to, (anode/cathode) couples:(LiC₆/AgF_(x)), (LiC₆/NiF_(x)), (Li_(x)Si/CF_(x)), and(Li)_(n)Si/CuF_(x)).

Aspects of the present invention are further set forth and described inthe following Examples.

Example 1 Fluoride Ion Secondary Electrochemical Cell with Li/CFx HalfCell Configurations

1.a. Introduction.

To demonstrate the benefits of the present fluoride ion electrochemicalcells, cells comprising a CF_(x) positive electrode and metallic lithiumnegative electrode were constructed and evaluated with respect toelectrochemical performance. The results shown here demonstrate thatfluoride ion electrochemical cells exhibit useful rechargeablecapacities under reasonable charge-discharge rates at room temperatures.

1.b. Experimental.

Two types of carbon fluorides CF_(x) were synthesized and used aspositive electrodes in lithium cells in this example; 1) stoichiometric(commercial) CF₁ based on coke and, 2) sub-fluorinated CF_(x) (x<1)based on graphite and multi-walled carbon nanotubes (MWNTs). Carbonfluoride is obtained from high temperature fluorination of coke graphiteor MWNT carbon powders, following reaction:

C(s)+x/2F₂(g)→CF_(x)(s) (s=solid and g=gas)

Several kinds of fully fluorinated and subfluorinated carbon, referredto as CF_(x), were investigated in the present example for use as theactive material for the positive electrode:

-   (1) Commercial CFx (wherein x=1.0); This subfluorinated    carbonanceous material was obtained from Lodestar, N.Y., USA, and    corresponds to their PC10 product which is a fully fluorinated coke    material. This subfluorinated carbonanceous material is synonymously    referred to as “commercial”, “commercial CFx”, and “CFx (x=1)” in    the Figures and throughout this example;-   (2) Subfluorinated carbon synthesized by fluorination of synthetic    graphite (CFx wherein x=0.530, 0.647). This subfluorinated material    was synthesized via partial fluorination of synthetic graphite    produced by Timcal, Switzerland. These subfluorinated graphite    materials are referred to as “KS15” in the figures and throughout    this example. The compositions of these materials are further    characterized by reference to the atomic ratio of fluorine to carbon    (i.e., the variable x in the formula CFx); and-   (3) Subfluorinated carbons synthesized by fluorination of    multiwalled carbon nanotubes (MWNTs), (CFx wherein x=0.21, 0.59,    0.76, 0.82). This subfluorinated material was synthesized via    partial fluorination of MWNTS obtained from MER, Tucson, Ariz., USA.    This subfluorinated material is synonymously referred to as “carbon    nanofiber”, “MWNT” and “multiwalled carbon nanotubes” in the figures    and throughout this example. The compositions of these    subfluorinated carbonaceous materials are further characterized by    reference to the atomic ratio of fluorine to carbon (i.e., the    variable x in the formula CFx)

The positive electrode consisted of a selected CF_(x) material with theaddition of Acetylene Black Graphite (ABG) and PVDF as a binder, withrespective percentages of 75 wt %, 10 wt % and 15 wt %. These threematerials were mixed together in Acetone solution with dibutyl phthalateDBP (20 wt %). The solution was then evaporated and finally, a thin filmof CF_(x) positive electrode was obtained (100-120 μm thick). The filmwas cut to diameter (15.2 mm) and washed in Methanol and dried at 80° C.overnight in vacuum. The electrode weight is 10˜20 mg. Structure of cointype Li/CF_(x) test batteries; Li/PC-DME-LiBF₄/CF_(x), 2016 coin cells.(Separator; Sanyo Celgard, diameter (19 mm), thickness (25 μm), strong,low electrical resistivity and high porosity (55%).)

1.c. Experimental Results

FIG. 4 provides crystal structure of carbon fluoride. FIG. 5 provides-ray diffraction patterns (CuK_(α) □radiation) from various positiveelectrode materials evaluated comprising commercial CF₁ and varioussubfluorinated carbonaceous materials. Diffraction patterns for avariety of subfluorinated carbon nanofiber samples (i.e., MWNTs, CFx;x=0.210, 0.590, 0.760 and 0.820), a variety of subfluorinated KS15graphite samples (i.e., CFx; x=0.53 and 0.647); and commercial CF₁sample (i.e.; CFx, x=1) are shown in FIG. 5.

The various fluorinated carbon active materials were also characterizedvia electrochemical methods. In these experiments, CyclicChronopotentiometry (constant current) is used to follow the dischargeand charge of cells. The applied current calculated from the theoreticalcapacity. Thus, for different fixed C/n rate (C/10˜1 C), one candetermine the current I:

$I = {\frac{C}{n} = \frac{m_{CFx} \times {Q_{th}(x)}}{n}}$${Q_{th}(x)} = {\frac{96500x}{3.6\left( {12 + {19x}} \right)}\left( {{{mA}h}\text{/}g} \right)}$

m_(CFx)=mass of active material (g), Q_(th)=theoretical capacity inmAh/gNote: Q_(th) is expressed in mAh/g of CF_(x) during the first dischargeand in mAh/g of C during cycling

In these measurements, the first discharge and subsequent cyclingreactions were as follows:

First Discharge

CF_(x)+Li⁺ +xe ⁻→C+xLiF (3.2V-1.5V vs. Li)

Cycling Reaction

C+yA⁻

CA_(y) +ye ⁻ (1.5V-up to 4.8V vs. Li) (A⁻=anion=F⁻)

FIGS. 6-12 provides first discharge curves for a number of positiveelectrode carbonaceous active materials. FIG. 6 provides dischargeprofiles for commercial CF₁ positive electrodes at room temperature fora variety of discharge rates ranging from C/20 to C. FIG. 7 providesdischarge profiles for CF_(0.530), KS15 positive electrodes at roomtemperature for a variety of discharge rates ranging from C/20 to C.FIG. 8 provides discharge profiles for CF_(0.647), KS15 positiveelectrodes at room temperature for a variety of discharge rates rangingfrom C/20 to 6 C. FIG. 9 provides discharge profiles for CF_(0.21),carbon nanofiber positive electrodes at room temperature for a varietyof discharge rates ranging from C/20 to 6 C. FIG. 10 provides dischargeprofiles for CF_(0.59), carbon nanofiber positive electrodes at roomtemperature for a variety of discharge rates ranging from C/20 to 6 C.FIG. 11 provides discharge profiles for CF_(0.76), carbon nanofiberpositive electrodes at room temperature for a variety of discharge ratesranging from C/20 to 6 C. FIG. 12 provides discharge profiles forCF_(0.82), carbon nanofiber positive electrodes at room temperature fora variety of discharge rates ranging from C/20 to 4 C. The observeddischarge profiles are consistent with a first discharge cell reactionof:

CF_(x)+Li⁺ +xe ⁻→C+xLiF (3.2V-1.5V vs. Li).

FIGS. 13-15 provide plots showing cycling tests for several positiveelectrode carbonaceous active materials. FIG. 13 providescharge-discharge profiles for CF_(0.82), multiwalled nanotubes positiveelectrodes for a voltage range 1.5V to 4.6V. Voltage is plotted on the Yaxis (left side), Current is plotted on the Y axis (right side) and timeis plotted on the X axis. FIG. 14 provides charge-discharge profiles forCF_(0.82), multiwalled nanotubes positive electrodes for a voltage range1.5V to 4.8V. Voltage is plotted on the Y axis (left side), Current isplotted on the Y axis (right side) and time is plotted on the X axis.FIG. 15 provides charge-discharge profiles for CF₁ positive electrodesfor a voltage range 1.5V to 4.8V. Voltage is plotted on the Y axis (leftside), Current is plotted on the Y axis (right side) and time is plottedon the X axis. These figures show that the positive electrode materialsexamined, particularly CF_(x); x=0.82, MWNT (see, FIGS. 13 and 14), havethe ability to cycle and exhibit a stable cycle capacity. FIG. 16provides plots of voltage (V) vs. time (hours) for a Li/CF_(x) half cellconfiguration having a CF_(x); x=0.82, MWNT positive electrode for 4.6Vand 4.8V. An increase in discharge capacity of 0.25% is observedcorresponding to an increase in charging voltage from 4.6V to 4.8V. FIG.17 provides plots of voltage (V) vs relative capacity (%) for aLi/CF_(x) half cell configuration having a CF_(0.647) KS15 positiveelectrode for voltages ranging from 4.8V and 5.4V. As shown in FIG. 17,the CF_(0.647) KS15 positive electrode capacity increased with highercharge cutoff voltage over the range of 4.8V to 5.4V. FIGS. 16 and 17show a measurable increase in discharge capacity resulting from anincrease in charge voltage for the CFx materials examined. The observedcharge-discharge profiles shown in FIGS. 13-17 are consistent with acycling cell reaction of: C+yA⁻

CA_(y)+ye⁻ (1.5V-up to 4.8V vs. Li) (A⁻=anion=F⁻), and demonstrate thatLi⁺ is not participating in the cycling reactions.

FIG. 18 provides cycle capacity curves of discharge capacity (mAh/g-C)verse cycle number for various positive electrode materials evaluatedinclude commercial CF₁, subfluorinated KS15 graphite (CFx, x=0.53 &0.647) and subfluorinated MWNTs (CFx; x=0.21, 0.59, 0.76 and 0.82). Thecharging voltage for these measurements was 4.6 V, with the exception ofthe top most plot (dotted and dashed line) which corresponds to a chargevoltage of 4.8V and a positive electrode having an active materialcomprising subfluorinated MWNTs with CFx, X=0.82. Similar to thecharge-discharge profiles shown in FIGS. 16 and 17, a significantincrease in discharge capacity is observed for subfluorinated MWNTs withCFx, X=0.82 upon increasing the charging voltage from 4.6 V to 4.8V.

As shown in FIG. 18, the cell configuration having a commercial CF₁active positive electrode material does not exhibit very good cycling,most likely due to significant degradation in the structural integrityof CF₁ occurring during the first discharge. It is likely that theporosity of this positive electrode active material contributed to itsdegradation, which may have been caused by exfoliation initiated by thereaction between fluoride ions and lithium ions. In contrast, thesubfluorinated carbonaceous materials studied (e.g., graphite, MWNTs)exhibit very good cycling performance. This is likely due to the loweramount of fluorine and decreased porosity of these materials as comparedto commercial CFx, x=1. It is important to note that the subfluorinatedMWNTs provides the best cycling performance likely due to its greatermechanical integrity as compared to graphite and commercial CF₁.

The data in FIG. 18 demonstrates that 120 mAh/g-C rechargeable capacityhas been achieved in a Li/CF_(x) half cell configuration with a positiveelectrode having an active material comprising subfluorinated MWNTs withCFx, X=0.82 and charged to 4.8 V at a 2 C-rate. For the purpose ofcomparison, FIG. 20 provides a plot of the discharge rate capability fora LiMn₂O₄ positive electrode. These measurements show thatsub-fluorinated CF_(x) materials made of Multi-walled Carbon Nanotubesoutperform commercially available LiMn₂O₄ as positive electrodes inlithium rechargeable batteries.

FIG. 19 provides plots of discharge cycle vs. cycle number forCF_(0.82), multiwalled nanotubes positive electrodes for voltages equalto 4.6V to 4.8V. In these plots, discharge capacity (y-axis; mAh/g-C) isplots vs. cycle number in arbitrary units. FIG. 19 shows that stabledischarge characteristics are observed for this positive electrodeactive material for at least approximately 50 cycles.

To verify that fluoride ion was participating in the oxidation andreduction reactions at the electrode, X-ray diffraction patterns of thepositive electrode were acquired under different experimentalconditions. FIG. 21A provides a plot of discharge voltage vs timeindicating two time points (1) and (2) for which x-ray diffractionpatterns were taken. X-ray diffraction patterns Were also acquired forthe unused positive electrode. Thin graphite electrodes were used (50microns thick 3-4 mg). FIG. 21B shows x-ray diffraction patternsacquired at two time points (1) and (2) shown in FIG. 21A. FIG. 21Cshows x-ray diffraction patterns acquired at two time points (1) and (2)shown in FIG. 21A on an enlarge scale.

The diffraction patterns in FIGS. 21B and 21C corresponding to chargingto 5.2 V and subsequent discharge to 3.2 V show stage formation ofintercalated fluoride ions (a mixture of stage 2 and stage 3).Particularly, the appearance of the (002)-2, (003)-3 and (004)-3 peaksindicate that intercalated fluoride anions are present upon charging anddischarge. As shown by a comparison between the diffraction patternscorresponding to the unused positive electrode, the positive electrodeat 5.2V and the positive electrode at 3.2V, the graphite phasecompletely disappears upon charging to 5.2V and subsequently reappearsupon discharge to 3.2V. The C(002) graphite peak is present in thediffraction pattern corresponding to 3.2V shows that graphite is presentupon de-intercalation of the fluoride ions. Further, the sharp peakwidth of the C(002) graphite peak in the 3.2 V diffraction patternindicates that graphite maintains its structural integrity upon chargingand discharge. This result demonstrates that the fluoride ionintercalation and de-intercalation process is reversible and does notresult in a phase change from crystalline graphite to an amorphouscarbon phase. These result are consistent with a cycling cell reactionof:

C+yA⁻

CA_(y) +ye ⁻ (1.5V-up to 4.8V vs. Li) (A⁻=anion=F⁻),

and provide further evidence that that Li⁺ is not participating in thecycling reactions.

To further characterize the composition of the subfluorinated graphiteactive material for the positive electrode Electron Energy Loss Spectra(EELS) were acquired for conditions corresponding to charging theelectrochemical cell to 5.2 V. EELS is a useful for technique forcharacterizing the elemental composition of materials as it is verysensitive to the presence of elements in a sample and can identifyelements in a material very accurately. FIG. 22 provides an EELSspectrum of the positive electrode active material charged to 5.2V. Onlytwo peaks are shown in FIG. 22, and both of these peaks can be assignedto the presence of fluorine in the positive electrode active material.Peaks corresponding to other non-carbon elements, such as B or P, arenot present. This observation provides evidence that other anions in theelectrolyte, such as PF₆ ⁻ or BF₄ ⁻, were not intercalated.

1.d. Conclusions

Sub-fluorinated carbons materials, CF_(x), are excellent example of apositive electrode materials for fluorine anion rechargeable batteries.They show stable cycle life, high capacity, high discharge voltage andhigh rate capability. X-ray diffractometry coupled with electron energyloss spectrometry show that charge carrier fluoride anions do reversiblyintercalate into the carbon matrix, whether the later consists ofgraphite, coke or multiwalled carbon nanotube. Staging occurs, whichdraws similarity of fluorine anion intercalation with lithium cationintercalation in Li_(x)C₆ negative electrodes. Fluorine anion storagecapacity increases with charge cutoff voltage by about 150% between 4.5Vand 5.5V.

Example 2 Anion and Cation Receptors for Fluoride Ion ElectrochemicalCells

This example provides summary of anion and cation receptors useful inthe present invention. A number of fluoride ion receptors arespecifically exemplified that are capable of enhancing solubility offluoride salts and capable of enhancing the ionic conductive ofelectroyles in electrochemical cells of the present invention.

In an embodiment, an electrolyte of the present invention comprises ananion receptor having the chemical structure AR1:

wherein R₁, R₂ and R₃ are independently selected from the groupconsisting of alkyl, aromatic, ether, thioether, heterocyclic, aryl orheteroaryl groups which are optionally substituted with one or morehalogens, including F, alkyl, alkoxide, thiol, thioalkoxide, aromatic,ether or thioether.

In an embodiment, an electrolyte of the present invention comprises aborate-based anion receptor compound having the chemical structure AR2:

wherein R₄, R₅ and R₆ are selected from the group consisting of alkyl,aromatic, heterocyclic, aryl or heteroaryl groups which are optionallysubstituted with one or more halogens, including F, alkyl, alkoxide,thiol, thioalkoxide, aromatic, ether or thioether. In an embodiment R₄,R₅ and R₆ are identical. In an embodiment, each of R₄, R₅ and R₆ areF-bearing moieties.

In an embodiment, an electrolyte of the present invention comprises aphenyl boron-based anion receptor compound having the chemical structureAR3:

wherein R₇ and R₈ are selected from the group consisting of alkyl,aromatic, heterocyclic, aryl or heteroaryl groups which are optionallysubstituted with one or more halogens, including F, alkyl, alkoxide,thiol, thioalkoxide, aromatic, ether or thioether. In an embodiment R₇and R₈ are identical. In an embodiment, each of R₇ and R₈ are F-bearingmoieties. In an embodiment, R₇ and R₈ together from an aromatic,including a phenyl that is optionally substituted, includingsubstituents that are F and substituents that are themselves F-bearingmoieties, as shown by chemical formula AR4:

wherein X_(A) and X_(B) represent one or more hydrogens or non-hydrogenring substituents independently selected from the group consisting ofhalogens, including F, alkyl, alkoxide, thiol, thioalkoxide, ether,thioether. In an embodiment, at least one of the substituents is aF-bearing moiety.

In an embodiment, an electrolyte of the present invention comprises aTris (hexafluoroisopropyl) borate (THFIB; MW=511.9 AMU) anion receptorhaving the chemical structure AR5:

or a Tris (2,2,2-trifluoroethyl) borate (TTFEB; MW=307.9 AMU) anionreceptor having the chemical structure AR6:

or a Tris (pentafluorophenyl) borate (TPFPB; MW=511.98 AMU) anionreceptor having the chemical structure AR7:

or a Bis (1,1,3,3,3-hexafluoroisopropyl) pentafluorophenyl boronate(BHFIPFPB; MW—480.8 AMU) anion receptor having the structure AR8:

Anion receptors useful in electrolytes of present invention include, butare not limited to, those having the formula selected from the groupconsisting of: (CH₃O)₃B, (CF₃CH₂O)₃B, (C₃F₇CH₂O)₃B, [(CF₃)₂CHO]₃B,[(CF₃)₂C(C₆H₅)O]₃B, ((CF₃)CO)₃B, (C₆H₅O)₃B, (FC₆H₄O)₃B, (F₂C₆H₃O)₃B,(F₄C₆HO)₃B, (C₆F₅O)₃B, (CF₃C₆H₄O)₃B, [(CF₃)₂C₆H₃O]₃B and (C₆F₅)₃B.

Useful cation receptors in the present invention include, but are notlimited to, crown ethers, lariat ethers, metallacrown ethers,calixcrowns (e.g., calyx(aza)crowns), tetrathiafulvalene crowns,calixarenes, calix[4]arenediquinoes, tetrathiafulvalenes,bis(calixcrown)tetrathiafulvalenes, and derivatives thereof.

The following references describe anion and/or cation receptors usefulin embodiments of the present invention, and are hereby incorporated byreference to the extent not inconsistent with the present disclosure:(1) Evidence for Cryptand-like Behavior in Bibracchial Lariat Ether(BiBLE) Complexes Obtained from X-ray Crystallography and SolutionThermodynamic Studies, Kristin A. Arnold, Luis echeogoyen, Frank R.Fronczek, Richard D. Grandour, Vinicent J. Gatto, Banita D. White,George W. Gokel, J. Am. Chem. Soc., 109:3716-3721, 1987; (2)Bis(calixcrown)tetrathiafulvalene Receptors. Maria-Jesus Blesa, Bang-TunZhao, Magali Allain, Franck Le Derf, Marc Salle, Chem. Eur. J.12:1906-1914, 2006; (3) Studies on Calix(aza)crowns, II. Synthesis ofNovel Proximal Doubly Bridged Calix[4]arenes by Intramolecular ringClosure of syn 1,3- and 1,2- to ω-Chloraolkylamides, Istavan Bitter,Alajos Grun, Gabor Toth, Barbara Balazs, Gyula Horvath, Laszlo Toke,Tegrahedron 54:3857-3870, 1998; (4) Tetrathiafulvalene Crowns: RedoxSwitchable Ligands, Franck Le Derf, Miloud Mazari, Nicolas Mercier, EricLevillain, Gaelle Trippe, Amedee Riou, Pascal Richomme, Jan Becher,Javier Garin, Jesus Orduna, Nuria Gallego-Planas, Alain Gorgues, MarcSalle, Chem. Eur. J. 7, 2:447-455, 2001; (5) Electrochemical Behavior ofCalix[4]arenediquinones and Their Cation Binding Properties, Taek DongChung, Dongsuk Choi, Sun Kil Kang, Sang Swon Lee, Suk-Kyu Chang, HasuckKim, Journal of Electroanalytical Chemistry, 396:431-439, 1995; (6)Experimental Evidence for Alkali Metal Cation—π Interactions, George W.Gokel, Stephen L. De Wall, Eric S. Meadows, Eur. J. Chem, 2967-2978,2000; (7) π-Electron Properties of Large Condensed PolyaromaticHydrocarbons, S. E. Stein, R. L. Brown, J. Am. Chem. Soc.,109:3721-3729, 1987; (8) Self-Assembled Organometallic[12]Metallacrown-3 Complexes, Holger Piotrowski, Gerhard Hilt, AxelSchulz, Peter Mayer, Kurt Polborn, Kay Severin, Chem. Eur. J., 7,15:3197-3207, 2001; (9) First- and Second-sphere Coordination Chemistryof Alkali Metal Crown Ether Complexes, Jonathan W. Steed, CoordinationChemistry Reviews 215:171-221, 2001; (10) Alkali metal ion complexes offunctionalized calixarenes—competition between pendent arm and anionbond to sodium; R. Abidi, L. Baklouti, J. Harrowfield, A. Sobolev; J.Vicens, and A. White, Org. Biomol. Chem., 2003, 1, 3144-3146; (11)Transition Metal and Organometallic Anion Complexation Agents, Paul D.Beer, Elizabeth J. Hayes, Coordination Chemistry Review, 240:167-189,2003; (12) Versatile Self-Complexing Compounds Based on CovalentlyLinked Donor-Acceptor Cyclophanes, Yi Liu, Amar H. Flood, Ross M.Moskowitz, J. Fraser Stoddart, Chem. Eur. J. 11:369-385, 2005; (13)Study of Interactions of Various Ionic Species with Solvents Toward theDesign of Receptors, N. Jiten singh, Adriana C. Olleta, Anupriya Kumar,Mina Park, Hai-Bo Yi, Indrajit Bandyopadhyay, Han Myoung Lee, P.Tarakeshwar, Kwang S. Kim, Theor. Chem. Acc. 115:127-135, 2006; (14) ACalixarene-amide-tetrathiafulvalene Assembly for the ElectrochemicalDetection of Anions, Bang-Tun Zhao, Maria-Jesus Blesa, Nicolas Mercier,Franck Le Derf, Marc Salle, New J. Chem. 29:1164-1167, 2005.

STATEMENTS REGARDING INCORPORATION BY REFERENCE AND VARIATIONS

All references throughout this application, for example patent documentsincluding issued or granted patents or equivalents; patent applicationpublications; and non-patent literature documents or other sourcematerial; are hereby incorporated by reference herein in theirentireties, as though individually incorporated by reference, to theextent each reference is at least partially not inconsistent with thedisclosure in this application (for example, a reference that ispartially inconsistent is incorporated by reference except for thepartially inconsistent portion of the reference).

The terms and expressions which have been employed herein are used asterms of description and not of limitation, and there is no intention inthe use of such terms and expressions of excluding any equivalents ofthe features shown and described or portions thereof, but it isrecognized that various modifications are possible within the scope ofthe invention claimed. Thus, it should be understood that although thepresent invention has been specifically disclosed by preferredembodiments, exemplary embodiments and optional features, modificationand variation of the concepts herein disclosed may be resorted to bythose skilled in the art, and that such modifications and variations areconsidered to be within the scope of this invention as defined by theappended claims. The specific embodiments provided herein are examplesof useful embodiments of the present invention and it will be apparentto one skilled in the art that the present invention may be carried outusing a large number of variations of the devices, device components,methods steps set forth in the present description. As will be obviousto one of skill in the art, methods and devices useful for the presentmethods can include a large number of optional composition andprocessing elements and steps.

When a group of substituents is disclosed herein, it is understood thatall individual members of that group and all subgroups, including anyisomers, enantiomers, and diastereomers of the group members, aredisclosed separately. When a Markush group or other grouping is usedherein, all individual members of the group and all combinations andsubcombinations possible of the group are intended to be individuallyincluded in the disclosure. When a compound is described herein suchthat a particular isomer, enantiomer or diastereomer of the compound isnot specified, for example, in a formula or in a chemical name, thatdescription is intended to include each isomers and enantiomer of thecompound described individual or in any combination. Additionally,unless otherwise specified, all isotopic variants of compounds disclosedherein are intended to be encompassed by the disclosure. For example, itwill be understood that any one or more hydrogens in a moleculedisclosed can be replaced with deuterium or tritium. Isotopic variantsof a molecule are generally useful as standards in assays for themolecule and in chemical and biological research related to the moleculeor its use. Methods for making such isotopic variants are known in theart. Specific names of compounds are intended to be exemplary, as it isknown that one of ordinary skill in the art can name the same compoundsdifferently.

Many of the molecules disclosed herein contain one or more ionizablegroups [groups from which a proton can be removed (e.g., —COOH) or added(e.g., amines) or which can be quaternized (e.g., amines)]. All possibleionic forms of such molecules and salts thereof are intended to beincluded individually in the disclosure herein. With regard to salts ofthe compounds herein, one of ordinary skill in the art can select fromamong a wide variety of available counterions those that are appropriatefor preparation of salts of this invention for a given application. Inspecific applications, the selection of a given anion or cation forpreparation of a salt may result in increased or decreased solubility ofthat salt.

Every formulation or combination of components described or exemplifiedherein can be used to practice the invention, unless otherwise stated.

Whenever a range is given in the specification, for example, atemperature range, a time range, or a composition or concentrationrange, all intermediate ranges and subranges, as well as all individualvalues included in the ranges given are intended to be included in thedisclosure. It will be understood that any subranges or individualvalues in a range or subrange that are included in the descriptionherein can be excluded from the claims herein.

All patents and publications mentioned in the specification areindicative of the levels of skill of those skilled in the art to whichthe invention pertains. References cited herein are incorporated byreference herein in their entirety to indicate the state of the art asof their publication or filing date and it is intended that thisinformation can be employed herein, if needed, to exclude specificembodiments that are in the prior art. For example, when composition ofmatter are claimed, it should be understood that compounds known andavailable in the art prior to Applicant's invention, including compoundsfor which an enabling disclosure is provided in the references citedherein, are not intended to be included in the composition of matterclaims herein.

As used herein, “comprising” is synonymous with “including,”“containing,” or “characterized by,” and is inclusive or open-ended anddoes not exclude additional, unrecited elements or method steps. As usedherein, “consisting of” excludes any element, step, or ingredient notspecified in the claim element. As used herein, “consisting essentiallyof” does not exclude materials or steps that do not materially affectthe basic and novel characteristics of the claim. In each instanceherein any of the terms “comprising”, “consisting essentially of” and“consisting of” may be replaced with either of the other two terms. Theinvention illustratively described herein suitably may be practiced inthe absence of any element or elements, limitation or limitations whichis not specifically disclosed herein.

One of ordinary skill in the art will appreciate that startingmaterials, biological materials, reagents, synthetic methods,purification methods, analytical methods, assay methods, and biologicalmethods other than those specifically exemplified can be employed in thepractice of the invention without resort to undue experimentation. Allart-known functional equivalents, of any such materials and methods areintended to be included in this invention. The terms and expressionswhich have been employed are used as terms of description and not oflimitation, and there is no intention that in the use of such terms andexpressions of excluding any equivalents of the features shown anddescribed or portions thereof, but it is recognized that variousmodifications are possible within the scope of the invention claimed.Thus, it should be understood that although the present invention hasbeen specifically disclosed by preferred embodiments and optionalfeatures, modification and variation of the concepts herein disclosedmay be resorted to by those skilled in the art, and that suchmodifications and variations are considered to be within the scope ofthis invention as defined by the appended claims.

We claim:
 1. An electrochemical cell comprising: a positive electrode; anegative electrode; and an electrolyte provided between said positiveelectrode and said negative electrode; said electrolyte capable ofconducting anion charge carriers; wherein said positive electrode andnegative electrode reversibly exchange said anion charge carriers withsaid electrolyte during charging or discharging of said electrochemicalcell.
 2. The electrochemical cell of claim 1 wherein said anion chargecarriers are fluoride ions (F⁻).
 3. The electrochemical cell of claim 2wherein said electrolyte comprises a solvent and a fluoride salt,wherein said fluoride salt is at least partially present in a dissolvedstate in said electrolyte, thereby generating said fluoride ions in saidelectrolyte.
 4. The electrochemical cell of claim 3 wherein saidfluoride salt has the formula MF_(n), wherein M is a metal, and n is aninteger greater than
 0. 5. The electrochemical cell of claim 4 wherein Mis an alkali metal or an alkaline earth metal.
 6. The electrochemicalcell of claim 4 wherein M is a metal other than lithium.
 7. Theelectrochemical cell of claim 4 wherein M is Na, K, or Rb.
 8. Theelectrochemical cell of claim 1 wherein said anion charge carriers areselected from the group consisting of: BF₄ ⁻, PF₆ ⁻, AsF₆ ⁻, SbF₆ ⁻,BiF₆ ⁻, AlF₄ ⁻, GaF₄ ⁻, InF₄ ⁻, TlF₄ ⁻, SiF₅ ⁻, GeF₅ ⁻, SnF₅ ⁻, PbF₅ ⁻,SF₇ ⁻, IF₆ ⁻, ClO₄ ⁻, CF₃SO₃ ⁻, (CF₃SO₂)₂N⁻ and C₄F₉SO₃ ⁻.
 9. Theelectrochemical cell of claim 1 wherein the anion charge carrier is ananion other than OH⁻ and HSO₄ ⁻, or SO₄ ²⁻.
 10. The electrochemical cellof claim 1 wherein said electrolyte further comprises an anion receptor.11. The electrochemical cell of claim 3 wherein said electrolyte furthercomprises a fluoride ion anion receptor capable of coordinating fluorideions from said fluoride salt.
 12. The electrochemical cell of claim 1wherein said electrolyte further comprises a cation receptor capable ofcoordinating metal ions from said fluoride salt.
 13. The electrochemicalcell of claim 1 wherein said electrolyte is an aqueous electrolyte. 14.The electrochemical cell of claim 1 wherein said electrolyte is anonaqueous electrolyte.
 15. The electrochemical cell of claim 1 whereinsaid anion charge carriers are fluoride ions (F⁻), and wherein saidnegative electrode is a fluoride ion host material.
 16. Theelectrochemical cell of claim 15 wherein said fluoride ion host materialof said negative electrode is a fluoride compound.
 17. Theelectrochemical cell of claim 15 wherein said fluoride ion host materialof said negative electrode is selected from the group consisting of:LaF_(x), CaF_(x), AlF_(x), EuF_(x), LiC₆, Li_(x)Si, Li_(x)Ge,Li_(x)(CoTiSn), SnF_(x), InF_(x), VF_(x), CdF_(x), CrF_(x), FeF_(x),ZnF_(x), GaF_(x), TiF_(x), NbF_(x), MnF_(x), YbF_(x), ZrF_(x), SmF_(x),LaF_(x) and CeF_(x).
 18. The electrochemical cell of claim 15 whereinsaid fluoride ion host material of said negative electrode is a polymerselected from the group consisting of: polyacetylene, polyaniline,polypyrrol, polythiophene and polyparaphenylene.
 19. The electrochemicalcell of claim 15 wherein said negative electrode has a standardelectrode potential less than or equal to −1 V.
 20. The electrochemicalcell of claim 15 wherein said negative electrode has a standardelectrode potential less than or equal to −2 V.